Determination of the remoteness of an event comprising the production of a cellulose-containing object for protecting an article from falsification

ABSTRACT

The invention relates a method for determining the time dating event of creation of an object made of a cellulose containing material and having on its surface areas with a coating and without coating, in which the results of measurements of the components of nuclear-magnetic resonance relaxation are used for determining the parameters of free induction signals and the density of protons in cellulose samples taken from the cellulose containing material surface layer with coated and uncoated areas, the value G of relative changes of the cellulose parameters are calculated using the formula: 
         G=K   2   /K   2   +Pr   2   /Pr   1 , 
     where: Pr 1  and Pr 2  is the density of protons in cellulose, on the area having no coating and the area with a coating, respectively, g/sm 3 10 6 ;
         K 1  and K 2  are the degrees of crystallinity of the cellulose, on the area having no coating and the area with a coating, respectively, specified by the formula:       

         K =1-5( T   2   *A   d   /T   2   * A   k ), 
     where: T 2M  and T 2  is the relaxation time of the short and long components of the free induction signal, respectively, in microseconds;
         A K  and A d  are the maximum amplitude of the short and long components of the free induction signal, respectively, degrees;   D is the time dating of object creation determined by the linear dependence G (D) of the value G on the changes of the parameters of the cellulose sample from the time dating D:       

         G ( D )=[( G   2   −G   1 )/Δ t]·D,  
 
     where: G 1   G 2  are the values of relative changes of the cellulose parameters in a relative units determined as mentioned above, through the given time interval Δt. 
     In this case the object is an article, its fragment, an area with a coating, a time dating event mark applied on the article. The method of protection of an article from falsification of time dating event of its creation is proposed, in which a mark is plotted on the article surface. The mark is made of a cellulose containing material and tightly fixed it on the article surface by means of a permanent connection providing destruction of the mark at its unauthorized removal from the article surface, and the external surface of the mark has areas without coating and with a coating applied when fixing the mark on the article surface.

FIELD OF INVENTION

The invention relates to a technical expert examination on determiningthe time dating event of creation of various types of objects made acellulose containing material or objects having on their surfacefragments of a cellulose containing material and having on the surfaceof the cellulose containing material at least one open area having nocoating, and at least one coated area. The invention also relates tomethods for determining the time dating event of application of acoating on said object or on said fragment.

In particular, the invention relates to a field of determinating thetime dating event of creating objects having on their surface an appliedimage made of paper, fabric, a papier-mache, wood in the form ofindustrial goods, articles of individual creativity and individual use,for example, printed matter, a souvenir article, a figurine, a piece offurniture, a loomwork, a hand weaving article, a picture, variousprinted and hand-written documents including coated areas, made bycoating the surface of a cellulose containing material with varioustypes of the coating materials applied by jet of another printingtechnique, contact technique, hand-writing or other methods: colouringagents, varnishes, mastics any art colours, printing inks, stampinginks, pastes (for example, those for ball pens), powders (for example,for cartridges of printing devices), ink (for example, for pen-type,capillary, gel and fountain pens, felt pens), biopolymeric ink for pens,and other coatings.

BACKGROUND OF THE INVENTION

In view of the wide use of cellulose which is a natural biopolymerhaving a complex structure and special physical and chemical properties,used for creation during the various historical periods of man activity,of objects of culture, author's right objects, individual creativityarticles, various constitutive documents, archive documents of privateuse and other objects and articles, a very important problem in thearchive, antiquarian, criminalistic and judicial activity consists inestablishing the correspondence of the claimed date of creation of anarticle, an object or its fragment to its true (valid) creation date.

At present there are known various methods for determining the age ofcellulose containing materials which, proceeding from estimation ofrespective changes in the physical and chemical properties and thecellulose structure under the environmental effects, said methods beingused for estimating the age of the object as a whole including an objecthaving on the surface of the cellulose containing material an imagewhich can be made of other materials during the various periods of thelife of the cellulose containing carrier.

Known in the art is a method for determining the age of a carrier madeof a based-cellulose material (RO, 116844), used for establishing thedate of writing of documents, mainly, in determination of theintervention process required for recovery and saving of manuscripts,products of the early period and old books by means of sampling anddetermination of the level of whiteness in the initial phase and afterthe heat treatment at 103 . . . 2 degrees centigrade.

Known in the art is a method for determining the age of a fabric made ofcellulose (RO, 121151,) for the purpose of determining the date ofcreation of a picture canvas, an article of clothing and old materialsby determining the degree of polymerisation of the cellulose using analkali solution of the Schweizer's reagent.

Known in the art is a method for determining the chemicalcharacteristics of cellulose in samples of paper by the content ofcarbonyl and carboxyl groups. (DE, 102007-44606, B4), in which there isstudied the content of the carbonyl groups decreasing with an increaseof the sample age, and the content of the carboxyl groups increasingwith an increase of the paper age because of progressive processes ofoxidation of the cellulose. The parameters of whiteness and density ofthe cellulose and paper can be found in the same way.

Known in the art is a method for determining the age of a documentwritten on paper, for example, a manuscript (DE 3603599, A1), in whichsmall samples of paper put in a solution for some time and thedissolving can be accelerated by means of ultrasonic treatment. From 5to 7 solutions are used one after another, then the obtained solutionsare subjected to a thin-layer chromatography to determine thedisappearance of colour in the solution and mathematically finding thenumerical value of the gradient of the resultant curve of theexponential function which is used as an index of the document age: ahigher curvature of the function corresponds to a younger document, andthe smaller one corresponds a more ancient document. However, thismethod does not allow one to compare the age of paper with the age ofthe applied colour coating that is required, for example, fordetermining forgeries and falsification of dates and signatures on thedocuments.

Known in the art is a method for determining the date of creation of oldmaterials made of cellulose-based fabrics (MD, 3325, F1) including:determination of the degree of polymerisation of the cellulose in an oldmaterial by the viscometric method, establishing the level ofdecomposition of the cellulose in the ratio (%)=100[2/(GP)_(i)−2/(GP)_(f)], where (GP)_(f) is the degree of polymerisationof the cellulose in the old material, and (GP)_(i)—is the degree ofpolymerisation of the cellulose in the new cotton or new cellulosemixture: flax, hemp and/or cotton equal, accordingly, to 1800 and 3100;extrapolation of the level of decomposition of the cellulose (%) ongraphics representing an age equivalent of the material depending on thelevel of decomposition of the cellulose using various graphics for thecotton and for said cellulose mixture.

Known in the art is a method for determining the dating of creation ofhandwritten texts and other written materials (RU, 2296315, C1), inwhich two samples of the written material being tested are obtained, oneof which is extracted by a solvent and the other one is first heated andthen extracted under the same conditions by the same solvent, thenquantitative comparison of the extraction results is made, before thequantitative comparison both samples being subjected tospectrophotometric analysis in which there is obtained a relation of theoptical densities in the field of maximum of peaks of the colouringagents per unit length a dash sample of each sample calculating theratio of the optical densities in the field from 400 to 1100 nanometers,and determining the time dating of the studied document made bycomparing these values with the similar parameters of this documentswith a certainly known date of their creation, presented in a graphicalor a tabular form.

Also known in the art are methods for determining the age of elements ofimages applied onto a carrier surface by which definition of the age ofthe document as a whole is made.

Known in the art is a method for determining the age of ink applied on aworking surface with respect to other signatures or symbols by a changeof the pH factor of the chemical compounds in the ink changing thecomposition in process of chemical reactions therein and correspondingto the age of the ink (U.S. Pat. No. 5,600,443).

Known in the art is a method for determining the age of hand-writtenfragments and texts made by a jet printing device, printing seals andthe stamps made by stamping inks using the method of gaschromatography—mass spectrometry (Aginsky V. N. <<Dating andCharacterizing Writing, Stamp Pad and Jet Printer Inks by GasChromatography/Mass Spectrometry>>, International Journal of ForensicDocument Examiners, Vol. 2, No. 3, July/September 1996, p. 103-116).This method is based on the dependence between the age of dash samplesand the content in the dash samples of high-boiling organic solvents.The study includes extraction of the solvent from the tested dash sampleat first with a “weak” extragent, and then with a “strong” extragent,and determination of the level of extraction of the solvent from thedash sample which decreases with the dash sample age. Then theaccelerated (artificial) aging of the tested dash samples is performed(heating to 70° C. within 4 hours) and determination of the level ofextraction of the solvent as described above. The main criterion at theestimation of the dash sample age in this method is the difference inthe characteristics of the level of extraction of the solvent obtainedbefore and after the artificial aging. The determination of thedifference of the level of extraction of the solvent is based on thequantitative analysis of the solvent extracted from the tested dashsamples by the method of gas chromatography—mass spectrometry using theinternal standard. However, the method takes no account of the effect ofthe following factors: the compositions of the main components of thecolorant in the studied dash samples, the character of its allocation inthe compared dash samples, the completeness of the surfacing the dashsample with extragents in the course of extraction, the nature of the“strong extragent”, the error of internal standard method whendetermining the amount of the solvent in the studied dash samples, whilein dash samples with an insignificant content of colorant can bedetermined mainly by the “background” content of solvent due to itsmigration from the dash sample to the other requisites.

Known in the art is a method for time dating the requisites in documentsby relative: content in their dash samples of volatile solvents (RU,2399042, C1), used in technical expert appraisal of documents fordetermining the authenticity and age of documents of different typeswhose requisites are made by a paste of ball pens, ink for gel pens, ajet printing method, and stamping inks A microscopic technique is usedfor determining the sort of material in a letter in the dash samples andthe fitness of the availability in the document for a further study. Atleast two objects of study are obtained in the form of samples foranalysis, one of which comprises the dash samples of the documentrequisites, and the other one is a piece of paper of the document freeof dash samples. Each sample for analysis is subjected to thermaldesorptions in a continuous gas flow for a certain time and at a giventemperature with formation of a mixture of a carrier gas and thermaldesorption products, then thermal desorption products are divided intoseparate substances. The results of the analysis of the samples of adash sample and/or paper are obtained in the form of a graphic curve,the presence and the amount of specific solvents in the dash sample aredetermined by the retention time and height of the peaks on the graphiccurve, the presence of thermal desorption products in the dash samplesis determined in the paper products with the same retention time, as theretention time of the solvents in the examined dash samples, by thegraphic curve. For the characteristic of the content of solvent in thedash sample there is taken the height of an appropriate peak on thegraphic curve—the dash sample chromatogram expressed in standard unitstaking into account the contribution of thermal desorption products fromthe paper being tested. Then the colorant is extracted from the dashsamples and the extracts obtained are subjected to a spectrophotometricanalysis in the visible range of spectrum for determining the content ofthe colouring agent in then sample in the form of a graphic curve of theabsorption spectrum of the obtained extract in a spectrophotometer.However, in said method the sample of paper is used for exclusion of theeffect of the products on thermal desorption of the paper on the resultof study of the solvents in thermal desorption products of the dashsample, and this method is technologically very complicated, because itrequires a significant amount of the reference data concerning theconnections constituting the paper material and the dash sample materialin initial state and in the process of their age changing.

However, determining the time dating event of creation of documents as awhole by the age change of the dash samples applied thereon is notauthentic since in the same document the dash samples can be applied atvarious times in different fields of the document, for example, in caseof local forgery. Besides, the study of the composition of the materialsof the dash samples is a challenge because the change of the compositionof these materials depends mainly on the conditions of plotting the dashsamples on the document and on the conditions of subsequent state of thedocuments: temperature conditions of the document storage, radiationeffects, steam effect and other factors.

As it is well known to specialists in the field of technical expertexamination, at the present time the most informative parameterscharacterising the change of properties of cellulose are:

-   -   a degree of crystallinity of the cellulose;    -   an average density of the amorphous regions;    -   a density of distribution of protons (amount of protons) in the        studied sample with respect to which various methods of their        determination are developed.

It is also known that cellulose is a natural biopolymer consisting ofcrystalline and amorphous regions. In the course of physical andchemical effects, the volume and amount of the crystalline regionsdecrease and, as a consequence, the volume and amount of the amorphousregions increases that affects the degree of crystallinity of thecellulose and the cellulose molecular structure state characterized bythe presence and density of proton distribution.

Thus, from the study of the cellulose structure by means of impulse NRMspectroscopy there is obtained a multistage NMR-relaxational functionconsisting of two components: a short high-relaxation component and longslow-relaxation component. It is well known that the structuralcharacteristics of cellulose are determined mainly by the shortcomponent of the relaxational function which carries information on thevolume-mass ratio of the crystalline and amorphous phases of the polymerthat allows one to determine not only the degree of crystallinity butalso to evaluate the average size of the crystalline and amorphousregions and their volumetric density.

It is also known that spin-spin relaxation time sensitively reacts tochanges in the molecular system in the elementary links of the cellulosemolecule: this amplitude of free induction signals (from here onreferred to as the FIS) and the values of time of the spin-spin andspin-lattice relaxation allow one to obtain information on the state andproperties of the cellulose when making the cellulose containingmaterial and when creating an object having the cellulose containingmaterial and on their change as a result of various physical andchemical effects during the life of the cellulose containing material.

Known in the art is a method for determining the degree crystallinity ofcellulose (SU 1749800), in which a tested sample is wetted at a certainair humidity during certain time, excited and registered, for example,by means of nuclear-magnetic resonance spectroscopy, signals of the freeinduction (FIS) protons of the tested sample and the water reference,determine the amplitude of the standard signal A_(s) and the amplitudeof the slowly relaxing component A_(OD) of the sample signal, and thedegree of crystallinity is determined from the relation

${K = \frac{\frac{m_{o} \cdot A_{\ni}}{m_{\ni} \cdot A_{OD}} - 1}{\frac{m_{o} \cdot A_{\ni}}{m_{\ni} \cdot A_{OD}} - 1 + \rho_{K}}},$

where m_(O) is the sample mass, g;

is the mass of the water reference, g; ρ_(k) is the density of thecrystalline regions of cellulose in the sample, g/cm³.

Known in the art is a method for determining the degree of crystallinityof natural polymers (RU 2175765, C1) including excitation and recordingof the characteristic signal of the tested sample, in which the testedsamples are wetted from 0 to hygroscopicity with a humidity fromtheoretically dry state to the hygroscopic state, and the characteristicsignal is registered by means of the impulse nuclear-magnetic resonancespectrometer (NMR H¹) of the free induction signal (FIS) of the drop ofprotons, then the FIS signal is used for determining the times of thespin-spin relaxation T_(2k) of the short component, the humiditydependencies T_(2k) are used for determining the characteristic timesT₂₀, T₂₁, T₂₂, T₂₃ and the degree of crystallinity K by the formula:

${K = {1 - \frac{\left( {T_{21} - T_{20}} \right) + \left( {T_{23} - T_{22}} \right)}{T_{20}}}},$

where T₂₀ is the time of the spin-spin relaxation of the short componentof theoretically dry sample;

T₂₁ is the time of the spin-spin relaxation of the short component atthe end of adsorption of the water molecules directly on the activecentres in the amorphous regions of the polymer sample:

T₂₂ is the time of spin-spin relaxation of the short component atfilling the monomolecular layer of the water molecules;

T₂₃ is the time of the spin-spin relaxation of the short component at ahygroscopic water content of the sample.

Known in the art is a method for determining proton-containingsubstances in the initial, intermediate and finished cellulose-basedproducts (RU 2053503, C1), in which the free induction signal (FIS) ofprotons is registered as a characteristic signal, the tested andreference samples of same mass are placed one after another in a sensorfor establishing the nuclear magnetic resonance, the samples areattacked by impulses, the amplitude of the short FIS component isrecorded from the initial and processed samples. After that there aredetermines the amplitudes A^(IK) and A^(EK) of the short components ofthe signals, accordingly, for the tested and reference samples, and thecrystallinity degree K is calculated using the formula:

K=1−(

.

/

.

),

where A^(H) and

are the amplitudes of the short component FIS of the tested andreference samples. respectively;

and

are respectively the masses of the reference and tested samples whichbeforehand were dried up to a constant mass.

However the estimation of the cellulose age by one parameter only is notcompletely justified because in one sample of an object or an articlethere can be areas of a cellulose containing material of variouscomposition, in a different degree of subject to the environmentaleffect, for example, in connection with the presence thereon ofprotecting coatings, for example, color agents, ink, varnishes. Besides,the time of application of coatings on various areas of the object maybe different and not corresponding to the time of initial creation ofthe document, and due to the mutual effect of their coating and thesubstrate determination of the age of a substrate made of a cellulosecontaining material including different types of cellulose and differentby the composition on the basis of study of one index is insufficient,and application of several methods of testing associated with samplingby distractive methods leads to damage of the document or article. Thusin the described method taking the samples leads to violation ofintegrity of the tested article.

Therefore, so far there are no methods of determination and criteria ofa simultaneous total estimation of parameters of the cellulosecharacterising the state of a cellulose containing material on differentareas of an object, both unprotected and protected in a different levelof environmental effects, thereby stipulating the age and time of theevent of application thereon of coatings, without a labour-consumingestimation of changes of the physical and chemical properties of theapplied coatings and without violation of the article integrity.

Therefore, the problem of creation of a method for determining the timedating event of object or article creation or its fragment made of acellulose-based materials and comprising different elements of coatings,and determining the time dating event of application of such coatings onthe surface of the cellulose containing material is very actual.

Besides, the problem of determining the time dating event of object orarticle creation is intimately connected to the problem of protection ofarticles from falsification of the data of their creation because theexisting methods of counterfeit detection are basically connected withtaking off a large enough sample of the article material that leads toviolation of its integrity, and also associated with a labour-intensiveprocess of studying the properties of the material and coating in theiraging and changing under the environmental effects.

SUMMARY OF THE INVENTION

An object to the invention is to develop a method for determining thetime dating of creation a cellulose containing article or an articlehaving on its surface fragments made of a cellulose containing materialand having surface areas with no coating and areas with a coating bymeans relative estimation of the changes in the properties of thecellulose in surface layer of the cellulose containing material atcreation of the article and its changed state after creation of thearticle and after application of the coating by means of measured andcalculated parameters determined at the moment of study taking intoaccount the dependence of such changes on the change of the coatingstate and on the varying conditions of the environment. Another objectis to create a mark to be applied on the article or on its fragmentduring their making, allowing one to identify the time of their creationwithout violating the integrity of the article and providing apossibility of protection of the articles against falsification of theirdating.

The objects of the invention have been attained by providing a methodfor determining the time dating of an object made of a cellulosecontaining material and having on its surface areas with a coating anduncoated areas, in which the results of the measurements of thecomponents of the nuclear-magnetic relaxational function of theparameters of the free induction signals and the density of protons inthe cellulose samples in the surface layer of the cellulose containingmaterial having an area with a coating and an area with no coating areused for calculating the value G of relative changes of the celluloseparameters using the formula:

G=K ₂ /K ₂ +Pr ₂ /Pr ₁,

where: Pr₁ and Pr₂ is the density of protons in cellulose, on the areahaving no coating and the area with a coating, respectively, g/sm³10⁶;

K₁ and K₂ are the degrees of crystallinity of the cellulose, on the areahaving no coating and the area with a coating, respectively, specifiedby the formula:

K=1-5(T _(2M) *A _(d) /T ₂ *A _(k)),

where: T_(2M) and T₂ is the relaxation time of the short and longcomponents of the free induction signal, respectively, in microseconds;

A_(K) and A_(d) are the maximum amplitude of the short and longcomponents of the free induction signal, respectively, degrees;

D is the time dating of object creation determined by the lineardependence G (D) of the value G on the changes of the parameters of thecellulose sample from the time dating D:

G(D)=[(G ₂ −G ₁)/Δt]·D,

where: G₁

G₂ are the values of relative changes of the cellulose parameters in arelative units determined as mentioned above, through the given timeinterval Δt.

Besides, according to the invention, it is possible to determine thetime dating event D of object creation by the results of comparison ofthe calculated values G with the values of the appropriate directcalibration dependence G (D) presented in a tabular or graphical formand based on experimental data.

In so doing, according to the invention, it is reasonable that in thesaid method for determining the time dating of object creation themeasurement of the components of the nuclear-magnetic relaxationalfunction, the parameters of the free induction signals and the time ofthe spin-spin and spin-lattice relaxation of the cellulose samples areperformed by means of the nuclear-magnetic resonance spectrometry.

In so doing, according to the invention, it is reasonable to use asample of a surface layer of the material of the area with a coatingtaken in the region of the greatest density of the coating.

Besides, according to the invention, it is reasonable to use samples ofa surface layer of the cellulose containing material having a minimumthickness of 0.05 mm and an area of not less than 0.3 MM ².

In so doing, according to the invention, it is reasonable to studysamples of the coated areas from the group including: colouring agents;varnishes; putties; art colors; typographical colours; stamp colors;pastes, for example, for ball pens; mastics, for example, for stamps;powders, for example, for cartridges of printing devices; ink, forexample, for pen, capillary, gel pens, fountain pens and felt pens;indian ink; biopolymeric ink for pens.

In so doing, according to the invention, it is possible that the objectis an article.

In so doing, according to the invention, it is possible that the objectis an area with a coating on an article surface.

In so doing, according to the invention, it is possible that the objectis a fragment of an article.

In so doing, according to the invention, it is possible that the objectis a mark for time dating event of object creation secured on thesurface of the article by means of permanent connection, and in themethod the dating event of creating the area with a coating on the marksurface is determined.

In so doing, according to the invention, it is possible that the methodis adapted for determining the time dating event of applying the markonto the surface of an article or its fragment.

In so doing, according to the invention, it is possible that the objectis made of a cellulose containing material including cellulose selectedfrom the group including cellulose from cotton, flax, hard wood and/orsoft wood, hemp, papyrus, bamboo, rice and wheaten straw.

In so doing, according to the invention, it is possible that the objectis made of paper.

In so doing, according to the invention, it is possible that the objectis made of paper selected from group including: offset paper, newspaper,advertisement paper, cream-laid paper, vellum paper, Chinese paper,coated paper, elephant paper, rice paper, tracing paper, pergamentpaper, a Whitman paper a blotting paper, toilet paper, parchment paper,watermarked paper, wall-paper.

Besides, according to the invention, it is possible that the object ismade of cellulose containing fibers.

In so doing, according to the invention, it is possible that the objectis made of woven or a knitted fabric selected from the group including:cottonous fabric, cotton cloth, rayon fabric, gobelin tapestry.

Besides, according to the invention, probably that the object has beenmade of a papier-mache.

Besides, according to the invention, probably that the object has beenmade of wood or wood-shaving materials.

Besides, the invention provides creation a dating mark made of acellulose containing material and adapted for fixing on article surfaceby means of a permanent connection providing destruction of the mark atits unauthorized removal from the article surface, and having on theexternal surface areas with no coating and with a coating applied whenfixing the mark on the article.

Thus, according to the invention, it is possible that the mark has beenmade of a cellulose containing material from the group including paper,fabric, and papier-mache.

Thus, according to the invention, it is possible that the mark has anarea with a coating selected from group including: colouring agents;varnishes; mastics; art colors; typographical colors; stamp colors;mastics, for example, for stamps; powders, for example, for cartridgesof printing devices; indian ink; biopolymeric ink for pens.

Besides, the invention provides a method of protection of an articlefrom falsification of its dating by plotting on the article surface amark allowing one to identify the date of its creation, in which use ismade of a dating mark on the article surface made of a cellulosecontaining material and fixed on the article surface by means of apermanent connection, said mark being destroyed at its unauthorizedremoval from the article surface, and provide availability on itsexternal surface of areas with no coating and with a coating appliedwhen fixing the mark on the article surface.

Thus, according to the invention, it is reasonable to use a mark made ofa cellulose containing material selected from the group including paper,fabric, papier-mache.

Thus, according to the invention, the coating on the surface of thefixed mark can be applied by means of a material selected from the groupincluding: colouring agents; varnishes; mastics; art colors;typographical colours; stamp colors; mastics; powders, for example, forcartridges of printing devices; indian ink; biopolymeric ink for pens.

Thus, according to the invention, the mark can be fixed on the articlesurface by means of an adhesive, varnish or paint.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention is further described by way of examples of realisation ofa method for determining the time dating event comprising celluloseaccording to the invention, and examples of making a mark for timedating the event of making an article, a method for protection of anarticles against falsification for time dating the event and appendeddrawings, in which:

FIGS. 1, 2 illustrate the sampling to be tested by the method accordingto the invention;

FIG. 3 are Examples of a curve G (D) for various objects made ofcellulose containing materials, obtained on the experimental data basis;

FIG. 4 is a scheme of plotting a calibration line G (D) anddeterminations of the time dating D by the calculated value G of therelative changes of cellulose parameters of areas with coating and areaswith no coating.

The given examples are not exhaustive and are not beyond the set ofclaims.

DETAILED DESCRIPTION OF THE INVENTION

It is well known that cellulose is a natural biopolymer. Thesupermolecular structure of cellulose is extremely complex, it isdetermined by the ratio of crystalline and amorphous regions, each fieldhaving specific heterogeneity and accessibility. Eventually, theenvironmental and physical and chemical effects result in structuralchanges of the cellulose, its amorphicity (loosening): the amount of thecrystalline regions decreases and, as a consequence, the area ofamorphous regions increases.

In so doing as mentioned above, from the study of the cellulosestructure by means of impulse nuclear-magnetic spectroscopy there werefound multiple stages of the NMR-relaxational of the function consistingof two components: a short fast-relaxing component and a longslowly-relaxing one. It is also known that the structuralcharacteristics of cellulose are mainly determined by the shortcomponent of the relaxational function which carries information on thevolume-mass dependence of the crystalline and amorphous phases of thepolymer that allows one to determine not only the degree ofcrystallinity, but also to estimate the average size of crystalline andamorphous regions, as well as their bulk density.

It is also known that the spin-spin relaxation time sensitively reactsto changes of the molecular system in the elemental links of thecellulose molecules: the measurement of the amplitude of a freeinduction signal (FIS) and the spin-spin and spin-lattice relaxationtime allow us to obtain information on the cellulose state andproperties and their change as a result of various physical and chemicaleffects.

On the basis of the modern concept of the nuclear-magnetic relaxation inmultiphase systems methods for determining specified key parameters onthe basis of measurements of the free induction signal (FIS), forexample, by means of impulse spectroscopy NMR have been developed.

Also it is known that the amount of protons depends on the state of thecellulose molecules: destruction of the molecules leads to release ofthe protons. In so doing the density Pr of distribution of protons isdetermined by the actual data of measurements by means of NMRspectroscopy.

Thus the key parameters characterising the microstructure of thecellulose and its derivatives, their physical and chemical state andchange of these cellulose properties are specified by:

-   -   the degree of crystallinity of the cellulose;    -   the density of distribution of protons (an amount of protons).

Known in the art is a method for determining the degree of crystallinityof cellulose from the results of measurements of the amplitude of thefree induction signal (FIS) and the time of the spin-spin andspin-lattice relaxation (NMR capability in the analysis of structuraland sorption properties of biopolymers. Grunin Ju. B., Smotrina T. V.,Grunin L Ju., Lezhnina M. M., Gogelashvili G. Sh., Grunina N. G.,Krasilnikova S. V., The State Mari Technical University, 1993) bycalculation using the formula:

K=1-5(T _(2M) .AD/T ₂ .A _(K)),  (1)

where: T_(2M) and T₂ are spin-spin relaxation times, accordingly,strongly connected and relatively weakly connected by a water sample, inmicroseconds,

A_(K) and A_(D) are the amplitudes of the short and long components ofthe free induction signal (FIS) with relaxation times T_(2M) and T₂,accordingly, degrees.

Experimentally by means of standard methods of NMR spectroscopy onimpulse NMR of the spectrograph of the company AVANCE AV300 (Germany)there have been specified values of parameters characterising a physicaland chemical and structural state of various types of initial rawcellulose for manufacture of a cellulose containing material as shown inTable 1, which can be used for carrying out a comparative analysis ofthe cellulose properties in the process of its aging under theenvironmental effects.

TABLE 1 Values of the physical and chemical and the structuralparameters Various types of original raw cellulose applied tomanufacture of cellulose containing materials. Type of raw cellulose ina cellulose containing material Unbleached Bleached Unbleached Refinedsulphate Cotton sulphite sulphite sulphite Parameter cellulose cellulosecellulose cellulose cellulose Relaxation time 59 60 65 58 62 of theshort FIS component, T_(2M), microseconds Relaxation time 1640 2000 15401470 1230 of the long FIS component, T2, microseconds Maximum 122 120131 127 114 amplitude of the short FIS component, A_(K), degree. Maximum137 160 148 153 110 amplitude of the long FIS component, A_(D), degrees.Calculated 0.798 0.8 0.76 0.755 0.757 degree of crystallinity, Krelative units

From the data given in Table 1 it follows that the initial virgincellulose obtained by various methods from different natural raw atpositioned distinction of values of amplitudes of a free inductionsignal (FIS) and the time of the spin-spin and spin-lattice relaxationhas almost identical degree of crystallinity K, determined in formula 1on the basis of the measurements made with the help of the impulse NMRspectroscopy that allow one to use the measurements of the amplitudesand the relaxation time of short and long FIS components as distinctivecharacteristics of the state and structure of cellulose of any type. Andit is clear that the results of these measurements characterize thestate and volume of crystalline and amorphous regions of cellulose.

The same parameters and for different other types of virgin celluloseused for obtaining of the cellulose containing materials can bedetermined in the same way.

For a long time the inventor had been studied a large quantity ofsamples of different objects and articles made of cellulose containingmaterials based on different types of cellulose having a general formula[C₆H₇O₂(IT)₃]_(n). In so doing articles and their fragments having onits surface various areas with different coatings with well known datingexceeding 15 days and kept under different conditions have been studied:under normal conditions or in premises with a known particular regime ofstorage, for example, in archives and in museums. In so doing differentobjects have been studied:

-   -   objects made of a cellulose containing material, in particular,        based on cellulose sulphate bleached, sulphate unbleached,        sulphite bleached and sulphite unbleached, obtained from        different natural sources of cellulose: from cotton, from wood        and a bark of coniferous or deciduous breeds, from rice and        wheaten straw, from a flax, straw, from the papyrus, from        bamboo, in the form of different articles, in particular, books,        booklets, newspapers, logs, posters, manuscripts, wall-paper,        cards, printed and hand-written letters, financial and notarial        documents with printed text and hand-written elements, made on        different cellulose containing paper: advertisement paper,        Whatman paper, vellum paper, cream-laid paper, watermarked        paper, newspaper, tracing paper, kraft paper, coated paper,        offset paper, pergament paper, blotting paper, rice paper,        elephant paper, toilet paper;    -   objects made of fibers, objects containing cellulose cottonous        or cellulose material; from wood of deciduous and coniferous        breed, in the form of different cottonous and rayon fabrics,        articles of clothes, articles of an interior, gobelin        tapestries;    -   objects made of papier-maches based on cellulose of different        types, in the form of souvenir articles, relief overlays on        picture frames, for furniture;    -   objects made of wood of coniferous and deciduous breeds in the        form of furniture articles, articles of an interior, a        sculpture;    -   objects of wood-shaving materials in the form of panels;    -   objects in the form of the time dating event of creation marks        on an article surface made of masses of papier-mache based on        cellulose of different types, then solidified in air, from paper        scrap, from a scrap of fabric and glued onto the surface,        varnish or colour on articles of marble, on a grounded canvas,        on the face and back of pictures painted by oil and water        colours, on wooden articles;

In so doing the objects in the form of articles and fragments hadsurface coated areas made by different contact methods, characterized bya different degree of filling of the surface layer of an articlematerial: by application on paper by the hand-written method, aletterpress printing, offset printing, stamping; by application on afabric by straight-line and sublimatic heat transfer printing, a manualmethod. In so doing the coatings have been selected from the groupincluding: colouring agents; varnishes; mastics; art colors includingoil, a water colour, gouache; typographical colours; colours and masticsstamp; pastes for ball pens; powders for cartridges of printing devices;ink for pen, capillary, gel, fountain pens and felt pens; indian ink;biopolymeric ink for pens.

Objects in the form of marks had a different shape and size in a rangeof 0.3 to 1.0 cm². In so doing the marks from a papier-mache materialhave been applied on the surface of articles in the form of round dropswith subsequent hardening of the papier-mache after in air andapplication of the coating on a part of their surface. The marks offabric and paper have been made in the form of strips on their part ofwhose surface the coating in the form of dash samples or circles hasbeen applied and fixed on the article surface by means of glue orvarnish or oil colour. In so doing the coating on all the marks has beenapplied by means of a material selected from the group including:colouring agents; varnishes; mastics; art colors; printing ink; stampcolors; mastics; powders, for example, for cartridges of printingdevices; indian ink; biopolymeric ink for pens.

In the course of carrying out the study for preparing the samples ofsurface layer of a cellulose containing material to be tested on coatedareas and on areas with no coating in the form of disks having adiameter in a range of 0.3 to 0.55 mm and a thickness of not less than0.01 mm by means of the tool of a pinching tool having an internalopening with a diameter no more than 0.6 mm. In so doing samples on thecoated areas where taken from the areas having the greatest density ofthe coating among all areas available on the object surface with onetype of the coating, and samples on the areas with no coating taken onthe areas neighbouring the coated areas, for example, as shown in FIG. 1and FIG. 2, where “a”, “c” and <<e>> are the areas of cutout of sampleson the coated areas of stamping ink, paste a ball pen ink and a tonerpowder, accordingly, <<b>> <<d>> and <<f>> are the areas of cutout ofsamples on the areas with no coating.

In the course of study called the objects to be tested under amicroscope for determining the areas for taking samples of a cellulosecontaining material of the area with the greatest density of thecoatings and the areas with no coatings.

Then a cellulose sample was extracted from each obtained sample of acellulose containing material under a microscope, each cellulose samplewas placed in an individual clean test tube and placed in an impulse NMRspectrometer. Using the well known methods of impulse nuclear-magneticspectrometry, the following measurements were made:

-   -   time T_(2M) of relaxation of the short FIS component;    -   time T₂ of relaxation of the long FIS component;    -   the maximum amplitude A_(D) of the long FIS component;    -   the maximum amplitude A_(K) of the short FIS component,    -   the density P_(r2) of protons in the cellulose on the area under        a coating, the density P_(r1) of protons in the cellulose on the        area having no coating.

On the basis of the results of said measurements obtained by directexport of the data with the NMR spectrometer, the degree ofcrystallinity K₁ of the cellulose on the area with no coating and degreeof crystallinity K₂ of on the area with a coating were calculated by theformula:

K=1-5(T _(2M) ·A _(D) /T ₂ ·A ^(K)),  (1)

where: T_(2M) is the relaxation time of the short FIS component,microseconds;

T₂ is the relaxation time of the long FIS component, microseconds;

A_(D) is the maximum amplitude of the long FIS component, degree;

A_(K) is the maximum amplitude of the short FIS component, degree.

Then there were calculated the relative value K₂/K₁ of degree ofcrystallinity K₂ of the cellulose area with a coating in comparison withthe degree of crystallinity K₁ of the cellulose in the area with nocoating which characterizes changes in the cellulose structure dependingon the environmental effects and the level of natural aging of thecellulose.

In addition, there was calculated the relative value P_(r2)/P_(r1) ofthe density P_(r2) of protons in the cellulose area with a coating, incomparison with the density P_(r1) of protons in cellulose area havingno coating, which also characterizes the changes in the cellulosestructure depending on the environmental effects and a degree of thenatural aging of the cellulose.

Then there was calculated the value G of relative changes of thiscellulose parameters characterising the changes in cellulose structuredepending on the environmental effects and a degree of the natural agingof the cellulose based on the changes in the degree of crystallinity Kand changes of the density P_(r) of protons for each tested sample ofthe cellulose containing material under the following formula accordingto the invention:

G=K ₂ /K ₁ +P _(r2) /P _(r1),  (2)

where:

K₁ is the degree of crystallinity of the cellulose area having nocoating, relative units;

K₂ is the degree of crystallinity of the cellulose area with a coating,relative units;

Pr₁ is the density of protons of the area having no coating, g/cm³·10⁶;

Pr₂ is the density of protons in the coated area, g/cm³·10⁶.

The above measurements and calculations were conducted for studyingobjects with a given periodicity six times a year in a 2-monthsinterval.

Based on the obtained values of G for each studied object whose timedating was known to the inventor, graphics were plotted in coordinates:on the axis <<y>>-G in relative units, on the <<x>> axis—time dating Dof the object corresponding to the time interval which has passed fromevent of creation of the tested object before the date of the conductedstudy, in months. As a unit for the <<x>> scale use can be made of othertime units, however, the most acceptable unit for determining thereliable values of the cellulose parameters and relative changes ofthese parameters is time in months.

In the course of the analysis of the results of measurements and bymathematical computations on the basis of the obtained experimental dataa linear dependence G (D) was found for all studied objects and thesamples having a different slope to the <<x>> axis depending on the typeand density of the coating and the gradient of speed of change of thecellulose parameters in time:

G(D)=[(G ₂ −G ₁)/Δt]·D,  (3)

where: G₁ and G₂ are the relative values of changes of the parameters ofthe tested cellulose samples, accordingly, in the previous andsubsequent studies, relative units;

At is the time interval between the previous and subsequent studies,months;

D is the time dating event of test object creation, months.

In this case, the dependence (G₂−G₁)/Δt characterizes the angle of slopeof the straight line G (D) to the <<x>> axis depending on the gradientof the relative changes in the cellulose parameters of coated areas incomparison with the changes of the cellulose parameters in the areaswith no coating that is conditioned by a change of the density andtransmittivity of the coating and processes decreasing the protection ofthe surface of the cellulose containing material from the externaleffects and degradation of the coating.

Besides, according to the invention, the time dating event D of objectcreation can be determined by the results of comparison of thecalculated values G with the values G on appropriate calibration line G(D) which may be presented in a tabular or graphical form on the basisof the experimental data.

FIG. 3 illustrates some dependencies G(_(D)) typical for various testedobjects made of cellulose containing materials determined by the methodaccording to the invention on the basis of experimental data, forexample, straight lines 1, 2 and 3 for the objects based on bleachedsulphite cellulose with coatings applied thereon:

-   -   straight line 1 represents dependence G=0.0369 D determined:    -   for an object made in the form of a document on offset paper and        having in the field a printed text made by means of a laser        printer with a powdery toner of black color;    -   for an object made in the form of a document on an offset paper        and having in the field graphical characters applied by ink for        a gel pen;    -   for an object made in the form of a picture by a china ink on        rice paper;    -   straight line 2 represents dependence G=0.0338 D, determined:    -   for an object made in the form of a document on an offset paper        and having in the field graphical characters, applied by ball        pen paste;    -   for an object made in the form of a picture made by gouache on a        Whatman paper;    -   for an object made in the form of a picture made by a water        color on a Whatman paper;    -   straight line 3 represents dependence G=0.0277 D, determined:    -   for an object made in the form of a document on laid paper        having an ink signature applied with a fountain pen;    -   for an object made in the form of a document on an elephant        paper having in the field an impress of a seal applied by        stamping ink.

Thus, the linear dependencies G(D) determined in formula 3 for eachtested object can be used as calibration lines and, according to theinvention, the measured cellulose parameters P_(r2), P_(r1), T_(2M),A_(D), T₂, A_(K) and the values K₂ and K₁ calculated by formula 1 can beused for copulation of the value G by formula 2 and on the calibrationline a point can be found that corresponding to this value G and havingappropriate time dating event D of creating a tested area with a coatingon the tested object, and in case of coincidence of the time datingevent D for all coated areas, a conclusion may be made on creation of anobject as a whole.

The scheme of building up a characteristic calibration line 4 fordetermining the time dating event of creation of each of the coatedareas of the tested objects and determination of D are shown on FIG. 4.For this purpose, at any place of a grid chart a segment G₂−G₁ wasplotted, the values G2 and G1 having been calculated by formula 2 on thebasis of the results of measurements at the second and first study(subsequent and previous), accordingly, and the segment ends were spacedfrom each other for a certain distance corresponding to the timeinterval Δt

the first

second studies of the area samples with and with no coating. slope ofsaid segment determined the angle of slope of the calibration line 4 tothe <<x>> axis with a peak at the point G=0 at D=0. The calibration line4 was then built up by the value G1 of the first study used as an expertestimation, on the calibration line 4 we found an appropriate point witha coordinate y=G1 and calculated its coordinate on the <<x>> axiscorresponding to the time dating event D of creation of a test area witha coating. If all coated areas have identical time dating event, aconclusion may be drawn the time dating of creation an object as awhole. If the time dating event of various areas was different, aconclusion may be made on interference in the object after itsinitiating creation.

The given comparison of the values G calculated by formula 2 for thecoated areas on the tested objects having time dating event D of theircreation known to the studies, and the values G obtained for this timedating event D of their creation from the experimental calibration lineand from formula 3 have shown the complete convergence of the results.

Thus, during the creation of the invention we have found dependenciesdetermining the degree of change of the properties and characteristic ofthe cellulose parameters with account of the degree of change of thecoatings with time allowed us to estimate the dating events of creationof individual areas and an article as a whole without study of coatingsthemselves but only on the basis of the studies of the celluloseparameters using them for comparative analysis of the coated anduncoated areas. In so doing the found dependencies have allowed us todevelop a method for determining a time dating event of creation ofobjects as articles comprising cellulose in the material of which thearticle is made, or comprising cellulose in individual fragments of thecellulose articles, or individual elements comprising cellulose andallocated on the surface of the article or its fragments.

Specialists in the field of technical investigation for criminalisticand judicial expertise understand that in the when the object is afragment of an article or a dating event mark of creation an articlemade of a cellulose containing material open areas with no coating andan area with a coating, it is possible to determine the time datingevent of creation of such a fragment or applying a mark on their areas.

In so doing, according to the invention, the fragment of the article ormark can be made integrally with the article or separately from thearticle and also made of a cellulose containing material or anothermaterials, and fixed to the article surface by permanent connection, forexample, by means of an adhesive that allows one to use such a fragmentor such a mark as an element identifying the time dating event ofarticle creation.

Thus, according to the invention, the mark can be made of papers,fabrics, papier-mache or other materials based on cellulose and havingan area with a coating, for example, a pointwise coating. The mark canbe made in the form of a volumetric or plane figure of a different shapewith an image including an element identified visually or under amicroscope, for example, in the form of a trade mark of the author of anarticle and/or a trade mark of the owner of an article and/or a trademark of the manufacturer or in the form of an identified index of thearticle.

Determining the time dating event of article creation by the date ofplotting the mark by the method according to the invention includingstudy of microscopic samples of the areas of the mark surface withoutits distraction allows one to determine the time dating event ofapplication of a coating on the mark surface in the form of an image andthe time dating event of plotting said mark on an article that allowsone to draw a conclusion on authenticity of the article or on theforgery made in a later period. Those skilled in the art understand thatthe use of such marks is important in antiquarian and museum activity,as well as in a notariate and at creation of historically importantdocuments which are subject to storage for an unlimited period.

Creation of a method for determining the time dating event of objectcreation according to the invention and creation of the mark accordingto the invention has resulted in creation of a method for protection ofan article against falsification of the time dating event of itscreation by plotting a mark on its surface allowing one to identify thedate of creation of the article, in which the time dating event ofcreation of the mark on the article surface made of a cellulosecontaining material and fixed to the article surface by means of apermanent connection providing distraction of the mark at itsunauthorized removal from the article surface, and provide the presenceon its external surface of some areas having no coating and areas with acoating applied when fixing the mark to the article surface, forexample, by means of an adhesive, a varnish or a paint.

The marks can be made of a cellulose containing material selected fromgroup including paper, fabric, papier-mache, and the coating on thesurface of the fixed mark can be applied by means of a material selectedfrom group including coloring agents; varnishes; mastics; color art;printing blacks; stamp colors; mastics; powders, for example, forcartridges of printing devices; indian ink; biopolymeric ink for pens.

The validity of the results of determining the time dating cellulose asit was determined by the inventor by means of standard techniques. Thefigurine had on the surface areas a coating in the form of imageelements made by color of unknown type and composition;

-   -   object No. 3 in the form of a gobelin tapestry made, as it was        determined by the inventor by means of standard techniques, of        threads bases on the cottonous fibers, colored by applying a        coloring agent on the surface with a varying density and having        screw weaving;    -   object No. 4 in the form of a furniture article made, as it is        determined by the inventor by means of standard techniques, of        wood of deciduous breed—beech and having on the front face a        lacquer coat of unknown composition and below an inlaid        insertion made of a cedar.

The results of the study of objects Nos. 1-4 and the results ofdetermining the time dating event of creation of the tested objects andthe time dating event of creation on their surface of coated areas bythe claimed method are presented in Tables 2 to 5.

TABLE 2 Example of determining the time dating event of No. 1 objectcreation and creations on coated areas thereon using the methodaccording to the invention Tested object No. 1 made of paper comprisingbleached sulphite cellulose, an area of the document having named dateof creation of the document of “Oct. 08, 2000” Reference: Area PrintedHand-written parameters of of an area text having signature made Impressof bleached sulphite of the docu- a paper by a ball pen a seal madecellulose used Measured and calculated ment having coating made of bluedark by dark blue at production of No. parameters no coating with tonercolour stamping ink the paper 1 The relaxation time of the 63/60 58/5964/65 61/63 65 short FIS component measured in the first study andmeasured in the second study T_(2M), microseconds 2 The relaxation timeof the 1110/1070 1570/1580 1450/1430 1216/1175 1540 long FIS componentmeasured in the first study/measured in second study, T₂, microsec 3 Themaximum amplitude of the  96/109 134/129 108/112 116/122 131 shortcomponent FIS measured in the first study and measured in the secondstudy, A_(K), degree 4 The maximum amplitude of the 130/149 148/147131/138 126/132 148 long component FIS measured in the first study andmeasured in the second study, A_(D), degree 5 The degree ofcrystallinity of 0.61347/0.62013 — — — 0.76 cellulose of the area havingno coating, calculated in the first study and calculated in the secondstudy, K₁, relative units 6 The degree of crystallinity of —0.79571/0.78723 0.73231/0.72003  0.7251/0.71005 — cellulose of the areawith a coating, calculated in the first study and calculated in thesecond study, K₂, relative units 7 The density of protons on the1.63730/1.58087 — — — — area having no coating, measured in the firststudy and measured in the second study, Pr,/cm³ · 10⁶ 8 The density ofprotons on the — 3.28716/3.47001 3.05370/3.12015 2.99983/3.13007 — areawith a coating, measured in the first study and measured in the secondstudy, Pr₂, g/cm³ · 10⁶ 9 The value of the relative changes —3.02409/3.05183 3.07957/3.10731 3.07924/3.10698 — of the parameters ofcellulose: G1, calculated by formula 2 in the first study/G₂ in _(the)second study, relative units 10 Time interval between the first 1 1   1    1    — and second study Δt, microsec 11

— 0.02774 0.02774 0.02774 — (G₂ − G₁)/t for plotting the calibrationline 12 Dating event of creation — 109/109 111/111 111/111 — determinedby formula 3 for the value G, calculated by formula 2 in the first studyand/determined by the calibration line D, months

Thus, as seen from Table 2, the claimed method was used for determiningin the tested object No. 1 the following:

-   -   time dating event of creation of printed text on paper        constituting 109 months,    -   time dating event of creation a signature on paper constituting        111 months,    -   time dating event of creation of an impress of a seal        constituting 111 months.

On the basis of the obtained results the following conclusions may bedrawn:

-   -   the signature and impress of a seal on the document have been        made nine years three months till the moment of the first expert        study;    -   the printed text on the document has been made nine years one        month till the moment of the first expert study;    -   hence, the signature and impress of a seal have been made 2        months prior to making the printed text, and    -   time dating event of document creation by the date of Aug. 10,        2000 stated on the document does not meet the actual date.

The comparison of the obtained calculation results with the time datingevents of creation of coated areas on the object comprising similarcellulose, obtained on the basis of the experimental data has showntheir convergence within one months.

TABLE 3 Example of application of the claimed method for determinatingthe time dating event for creation of object No.2 and creation of coatedareas thereon Tested object No. 2 in the form of a figurine made ofpapier- mache based on unbleached sulphate cellulose having on thesurface coated areas in the form of image elements made by color ofunknown type and composition Reference: parameters of unbleached Thearea The area sulphite The measured and having no The area with with ared cellulose used No calculated parameters coating a white coatingcoating in the article  1 The relaxation time of 45/42 57/56 60/58 62short FIS component measured in the first study and measured in thesecond study, T_(2M), microseconds  2 The relaxation time of 1050/960 1210/1170 1190/1176 1230 the lFIS component measured in the first studyand measured in the second study, T₂, microseconds  3 The maximum 62/5592/86 102/92  110 amplitude of short FIS component measured in the firststudy and measured in the second study, A_(K), degrees  4 The maximum93/89 112/103 106/105 114 amplitude of the long FIS component measuredin the first study and measured in the second study, A_(D), degrees  5The degree of 0.6785/ — — 0.8 crystallinity of the 0.6460 cellulose areahaving no coating, calculated in the first study and calculated in thesecond study, K₁, relative units  6 The degree of — 0.7133/ 0.7380/ —crystallinity of the 0.7132 0.7185 cellulose area with a coating,calculated in the first study and calculated in the second study, K₂,relative units  7 The density of protons 0.29154/ — — — on the uncoatedarea 0.32985 measured in the first study and measured in the secondstudy, Pr₁, g/cm³ 10⁶  8 The density of protons — 2.82464/ 1.95107/ — onthe coated area, 3.18957 3.2 measured in the first study and measured inthe second study, Pr₂, g/cm³ · 10⁶  9 The value of relative — 10.7400/10.7800/ — changes of cellulose 10.7738 10.8138 parameters: G1,calculated by formula 2 in the first study and G2, calculated in thesecond study, relative units 10 Time interval between 1 1 1 — the firstand the second studies, Δ t, micro- seconds 11 Coefficient (G₂/Δ t —0.0338 0.0338 — for plotting calibration line 12 The time dating event —318/318 319/319 — determined in formula 3 for the value G, calculated byformula 2 in the first study and determined by the calibration line, D,months

Thus, as shown in Table 3, the claimed method was used for determiningin object No. 2 the following:

-   -   the time dating event of creating an area with a white coating        constituting 318 months,    -   the time dating event of creating an area with a red coating        constituting 319 months.

On the basis of the obtained results the following conclusions may bedrawn:

-   -   the area with the white coating was made 26 years 6 months prior        to the moment of the first study;    -   the area with the red coating has been made 26 years 7 months        prior to the moment of the first study.

Hence, the area with the white coating has been made for one month laterthan the area with the red coating that can be associated with updatingthe coating; in general, object No. 2 in the form of a figurine made ofpapier-mache as a whole, can be dated by time 26 years 7 months beforethe first study.

TABLE 4 Example of application of the claimed method for determinatingthe time dating event for creation of object No.3 and coated areasthereon Tested object No.3 is made in the form of a gobelin tapestryweaved of yarn based on cotton fibers and having a coating with acoloring agents of unknown type and composition Reference: The area withthe parameters coating, made of unbleached The area with a low- The areasulphite The measured and having intensity red with a red cellulose usedNo calculated parameters no coating coloring agent coating in thearticle  1 The relaxation time 38/35 51/49 54/51 60 of the short FIScomponent measured in the first study and measured in the second study,T_(2M), microseconds  2 The relaxation time 1230/ 1960/1920 1980/19302000 of the long FIS 1160 component measured in the first study andmeasured in the second study, T₂, microseconds  3 The maximum 76/68116/110 117/110 120 amplitude of the short FIS component measured in thefirst study and measured in the second study, A_(K), degrees  4 Themaximum 89/83 142/139 145/137 160 amplitude of the long FIS componentmeasured in the first study and measured in the second study, A_(D),degrees  5 The degrees of 0.8191/ — — 0.8 crystallinity of the 0.8158cellulose area having no coating, calculated in the first study andcalculated in the second study, K₁, relative units  6 The degrees of —0.8407/ 0.8310/ — crystallinity of the 0.8387 0.8260 cellulose area witha coating, calculated in the first study and calculated in the secondstudy, K₂, relative units  7 The density of 0.16725/ — — — protons onthe area 0.15273 having no coating, measured in the first study andmeasured in the second study, Pr₁, g/cm³ · 10⁶  8 The density of —2.01933/ 2.02120/ — protons on the area 1.86066 1.86295 with a coating,measured in the first study and measured in the second study, Pr₂, g/cm³· 10⁶  9 The value of relative — 13.1001/ 13.0995/ — changes ofcellulose 13.2108 13.2102 parameters: G₁, calculated by formula 2 in thefirst study and G2, calculated in the second study, relative units 10Time interval 3 3 3 — between the first and second studies, Δt,microseconds 11 The coefficient — 0.0369 0.0369 — (G₂ − G₁)/Δ t forplotting the calibration line 12 The time dating event — 358/358 358/358— determined in formula 3 for the value G, calculated by formula 2 inthe first study and determined by the calibration line, D, months

Thus, as shown in Table 4, the claimed method was used for determiningin object No. 3:

-   -   the time dating event of creating an area with a low-intensity        red coating constituting 358 months,    -   the time dating event of creating an area with a low-intensity        yellow coating constituting 358 months.

On the basis of the obtained results the following conclusions may bedrawn:

-   -   the time dating event of creating an area with a low-intensity        red coating and time dating event of creating an area with a        low-intensity yellow coating are identical and constitute 29        years and 10 months, hence, the gobelin tapestry has been made        29 years and 10 months prior to the first study, and as a whole        object No. 3 can be dated by 29 years and 10 months before the        first study that completely corresponds to the information given        by the owner.

TABLE 5 Example of application of the claimed method for determinatingthe time dating event for creation of object No.4 and creation of coatedareas thereon Object No.4 is made in the form of a furniture articlelike a bureau made of wood of deciduous breed—beech, and has on itsfront face a lacquer coating of unknown composition and has an inlaidinsertion of cedar wood The area with Reference: an insertion parameterselement of wood The area The area of made of cellulose The measured andhaving no beech with a cedar with a used in the No. calculatedparameters coating lacquer coat lacquer coat article  1 The relaxationtime of the 53/48 56/62 68/71 75 short FIS component measured in thefirst study and measured in the second study, T_(2M), microseconds  2The relaxation time of the 1056/ 1150/1230 1340/1370 1430 long FIScomponent 1095 measured in the first study and measured in the secondstudy, T₂, microseconds  3 The maximum amplitude 55/57 85/89 90/93 96 ofthe short FIS component measured in the first study and measured in thesecond study, A_(K), degrees  4 The maximum amplitude 103/110 115/118120/122 127 of the long FIS component measured in the first study andmeasured in the second study, A_(D), degrees  5 The degrees of 0.63/0.53— — 0.8 crystallinity of the cellulose area having no coating,calculated in the first study and calculated in the second study, K₁,relative units  6 The degrees of — 0.733/0.665 0.661/0.660 —crystallinity of the cellulose area with a coating, calculated in thefirst study and calculated in the second study, K₂, relative units  7The density of protons on 0.370/ — — — the area having no 0.340 coating,measured in the first study and measured in the second study, Pr₁, g/cm³· 10⁶  8 The density of protons on — 3,2308/ 3,3750/ — the area with acoating, 3.0549 3.0578 measured in the first study and measured in thesecond study, Pr₂, g/cm³ · 10⁶  9 The value of the relative — 10.172/10.171/ — changes of the cellulose 10.240 10.239 parameters: G₁,calculated by formula 2 in the first study and G₂, calculated in thesecond study, relative units 10 Time interval between the 2 2 2 — firstand second studies, Δ t, microseconds 11 The coefficient — 0.0338 0.0338— (G₂ is G1) /Δ t for plotting the calibration line 12 The time datingcreation — 303/303 303/303 — event determined in formula 3 for the valueG, calculated by formula 2 in the first study and determined on thecalibration line, D, months

Thus, as shown in Table 5, the claimed method was used for determiningin object No. 3:

-   -   the time dating event of creation a beech area with a lacquer        coating constituting 303 months,    -   the time dating event of creation of an area with a cedar        insertion with a lacquer coating constituting 303 months.

On the basis of the obtained results a conclusion may be drawn that themethod for determining the time dating event of creation a cellulosecontaining object is simple and predetermines its applicability indifferent areas of activity, as well as for dispute resolutions byjudicial inquiry and investigations.

The time dating mark of event of article creation developed according tothe invention can be used in the claimed method for protection ofarticles from falsification of their date of creation for detecting suchfalsification by determining the time dating event of application ofsuch a mark on the article surface, coinciding with the date ofapplication of a coating on the mark, and also for determining the timedating event of interference in the article. It can find wideapplication at study of the time dating event of articles, for example,articles of a high art value, unique articles, antiquarian articles,second-hand rare issuing, and other articles.

The claimed method for determining the time dating event of creating anobject containing cellulose in comparison with the known methods fordetermining the age of cellulose containing material or coatings on thismaterial possesses the merits:

-   -   sufficiently high accuracy of the results: accuracy to one month        and in certain cases about several weeks;    -   independence of the study results on artificial aging of an        object;    -   independence of the study results on the changes of properties        of the coating applied on the object;    -   the absence of significant damage of the object when taking        samples: the samples are of a microscopic size;    -   a possibility of accumulating statistical and experimental data        for various technical expert examinations of objects comprising        fragments of a cellulose containing material with different        types of coatings;    -   a low threshold of determining the time dating events of object        creation—from 30 days;    -   a possibility of determining the time dating events of creation        of art works by providing the antiques with firmly fixed marks        indicating to any interference in them with a change of their        form or composition of cellulose contained therein, by the state        of the mark not corresponding to the time dating event of        application and not corresponding to cellulose parameters        predicted for such dating, changing in time in a definite manner        that allow one to find out falsifications of the time dating        event of creation the works of art.

The claimed method for determining the time dating event of creating anobject containing cellulose can be performed using well knowntechnological and measuring equipment, the time dating mark creation ofa mark on an article surface can be made by means of well knownprocessing methods from well known cellulose containing materials withcoatings made by means of known technologies and materials. The methodfor protection of an article from falsification of the time dating eventof its creation and the method for determining a time dating event ofcreation of objects containing cellulose can be used in differentspheres of activity of human beings.

1. A method for determining a time dating event of creation of object,made of a cellulose containing material and having on its surface areaswith a coating and without coating in which on the basis of the resultsof measurements of components of nuclear-magnetic resonance relaxation,parameters of free induction signals and density of protons in thecellulose samples taken from the cellulose containing material surfacelayer on the coated and uncoated area, count the value G of the relativechanges of the cellulose parameters are calculated by the formula;G=K ₂ /K ₁ +Pr ₂ /Pr ₁, where: Pr₁ and Pr₂ is the density of protons inthe cellulose on the area having no coating and the area with a coating,accordingly, g/cm³·10⁶; K₁ and K₂ the degrees of crystallinity of thecellulose on the area having no coating, accordingly, determined by theformula:K=1-5(T _(2M) *A _(D) /T ₂ *A _(k)), where: T_(2M) and T₂—is therelaxation time, accordingly, of the short and long components of thefree induction signal, microseconds; A_(K) A_(D) is the maximumamplitude of the short and long component, accordingly, of the freeinduction signal, degrees; and the time dating event D of objectcreation is calculated on the basis of the linear dependence of thevalue G of the relative changes of the cellulose parameters on thesample on the time dating D:G(D)=[(G ₂ −G ₁)/Δt]. D, where: G₁ and G₂ are the values of the relativechanges of the cellulose parameters, relative units, determined in theabove described way via a given time interval Δt.
 2. The methodaccording to claim 1, in which the time dating event D of objectcreation is determined by the results of comparison of the calculatedvalues G with the values of the appropriate direct calibrationdependence G (D), presented in a tabular or graphical form and based onthe experimental data.
 3. The method according to claim 1, in which themeasurement of said components and parameters of the cellulose samplesis performed with the help of the nuclear-magnetic resonancespectrometry.
 4. The method according to claim 1, in which use is madeof samples of the area surface layer with a coating taken in the regionof the highest density of the coating.
 5. The method according to claim1, in which use is made of the samples of the surface layer of thecellulose containing material use having a minimum thickness of 0.05 mmand an area of not less than 0.3 MM ².
 6. The method according to claim1, in which use is made of a sample of an area with a coating made bymeans of a material from the group including: colouring agents;varnishes; putties; art colours; typographical colours; colours stamp;pastes, for example, for ball pens; mastics, for example, for stamps;powders, for example, for cartridges of printing devices; ink, forexample, for common pens, capillary pens, gel pens, fountain pens andfelt pens; indian ink; biopolymeric ink for pens.
 7. The methodaccording to claim 1, in which the object is an article.
 8. The methodaccording to claim 1, in which object is an area with a coating on thearticle surface.
 9. The method according to claim 1, in which the objectis an article fragment.
 10. The method according to claim 1, in whichobject is a time dating mark of event its creation, said mark beingapplied on the surface of the article during its creation and secured onthe article surface by means of permanent connection and used fordetermining time dating event of creation of an area with a coating on amark surface.
 11. The method according to claim 10, in which the timedating event of plotting a mark on the surface of an article or itsfragment is determined.
 12. The method according to claim 1, in whichthe object is made of a material comprising cellulose, selected of thegroup including cellulose from cotton, flax, and wood of deciduousand/or coniferous breeds, helm, papyrus, bamboo, rice or wheaten straw.13. The method according to claim 12, in which the object is made ofpaper.
 14. The method according to claim 13, in which the object is madeof a paper selected from the group including: offset paper, newspaper,advertisement paper, cream-laid paper, vellum paper, Chinese paper,coated paper, elephant paper, rice paper, tracing paper, pergamentpaper, Whatman paper, blotting paper, toilet paper, parchment paper,watermarked paper, wall-paper.
 15. The method according to claim 12, inwhich the object is made of cellulose containing fibers.
 16. The methodaccording to claim 15, in which the object is made of woven or a knittedfabric selected from group including: a cottonous fabric, a cottoncloth, a rayon fabric, a gobelin tapestry.
 17. The method according toclaim 12, in which the object is made of a papier-mache.
 18. The methodaccording to claim 12, in which the object is made of wood orwood-shaving materials.
 19. The time dating mark of its creation on thearticle surface is made of a cellulose containing material and adaptedfor tight fixation on the article surface by means of permanentconnection providing destruction of the mark at its unauthorized removalfrom the article surface, said mark having on its external surface areaswithout coating and with a coating applied when the mark is fixed ontothe article.
 20. The mark according to claim 19, in which the cellulosecontaining material is selected from the group including paper, fabric,papier-mache.
 21. The mark according to claim 19, in which the coatingis made using a material selected from the group including colouringagents; varnishes; mastics; art colours; typographical colours; stampcolours; mastics; powders, for example, for cartridges of printingdevices; indian ink; biopolymeric ink for pens.
 22. A method ofprotection of an article from falsification of time dating event of itscreation by applying a mark on the article surface allowing one toidentify the date of its creation, in which use is made a mark of timedating event of its creation on the article surface, made of a cellulosecontaining material and tightly fixed on a article surface by means ofpermanent connection providing destruction of the mark at itsunauthorized removal from the article surface and providing on itsexternal surface some areas without coating and with a coating appliedwhen fixing the mark on the article surface.
 23. The method according toclaim 22, in which the mark is made of a cellulose containing materialselected from the group including paper, fabric, and papier-mache. 24.The method according to claim 22, in which the coating on the surface ofthe fixed mark is applied by means of a material selected from groupincluding colouring agents; varnishes; mastics; art colours;typographical colours; stamp colours; mastics; powders, for example, forcartridges of printing devices; indian ink; biopolymeric ink for pens.25. The method according to claim 22, in which the mark is fixed on thearticle by means of an adhesive, varnish or paint.